1. Field of the Invention
The present invention relates to compounds of the formula I ##STR2## where A is nitro, amino, halocarbonyl or halosulfonyl,
R is hydrogen, halogen, nitro, cyano, C.sub.1 -C.sub.4 -alkanoylamino, hydroxyl, C.sub.1 -C.sub.4 -alkoxy, substituted or unsubstituted phenoxy, mercapto, C.sub.1 -C.sub.4 -alkylthio, substituted or unsubstituted phenylthio, carboxyl, C.sub.1 -C.sub.4 -alkoxycarbonyl, substituted or unsubstituted phenoxycarbonyl, carbamoyl, hydroxy ulfonyl, C.sub.1 -C.sub.4 -alkylsulfonyl, substituted or unsubstituted phenylsulfonyl, sulfamoyl or trifluoromethyl or is C.sub.1 -C.sub.4 -alkyl which may be substituted by hydroxyl, C.sub.1 -C.sub.4 -alkoxy or halogen, and PA1 X and Y are each, independently of one another, halogen, hydroxysulfonyl, C.sub.1 -C.sub.4 -alkoxy or substituted or unsubstituted phenoxy, subject to the proviso that at least one of X and Y is halogen.
Where the 3-cyanoquinoline derivatives of the formula I have one or more hydroxysulfonyl radicals and/or a carboxyl radical, the definition is also to cover the salts thereof, in particular the alkali metal salts, e.g., the sodium or potassium salts.
Where the phenyl radicals which appear in the formula I are substituted, suitable substituents are C.sub.1 -C.sub.4 -alkyl, halogen, in particular fluorine, chlorine or bromine, or C.sub.1 -C.sub.4 -alkoxy.
R, X and Y in the formula I are, for example, fluorine, chlorine, bromine, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, phenoxy, 4-methylphenoxy, 2-chlorophenoxy, or 2,4-dichlorophenoxy.
R in the formula I can also be for example formylamino, acetylamino, propionylamino, butyrylamino, isobutyrylamino, methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, phenylthio, 2-ethylphenylthio, 4-fluorophenylthio, 4-methoxyphenylthio, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, sec-butoxycarbonyl, phenoxycarbonyl, 4-isopropylphenoxycarbonyl, 2-bromophenoxycarbonyl, 4-methoxyphenoxycarbonyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, 2-ethylphenylsulfonyl, 2,4-dichlorophenylsulfonyl, 4-isopropoxyphenylsulfonyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secbutyl, 2-chloroethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl or 2- or 3-hydroxypropyl.
Preference is given to cyanoquinolines of the formula I where X and Y are each fluorine or where one of X and Y is fluorine or chlorine and the other is hydroxysulfonyl.
Particular importance is given to compounds of the formula II ##STR3## where A is nitro or amino, and X and Y are each fluorine, chlorine or hydroxysulfonyl.
To prepare the compounds according to the invention, it is possible for example to react an isatoic anhydride of the formula III ##STR4## where A and R each have the above-mentioned meanings, with an alkyl cyanoacetate. The resulting 3-cyano-2,4-dihydroxyquinoline derivative can then be converted in a conventional manner, for example by reaction with phosphorus oxychloride, into the corresponding 2,4-dichloro compound.
The dichloro compound can then be converted with a metal fluoride, for example sodium fluoride or potassium fluoride, or with hydrogen fluoride into the corresponding 2,4-dichloro compound.
The dichloro and difluoro compounds can be subjected to a nucleophilic substitution reaction, for example with the sulfite anion or with a hydroxy compound such as methanol, ethanol or phenol, to give a compound according to the invention where a halogen atom has been replaced.
The introduction of some of the substituents A and R can also be carried out directly on 3-cyano-2,4-dihydroxyquinoline by electrophilic substitution. Examples are nitration and sulfonation.
The compounds according to the invention are suitable for use as the fiber-bonding sites of reactive dyes, as intermediates for active substances and, where A is amino, even as diazo components.
As fiber-bonding sites the quinoline compounds react with the hydroxyl groups of e.g. cellulose. In this reaction the radical X and/or Y which is halogen is replaced by an oxygen atom of a cellulose hydroxyl group. When both radicals X and Y are halogen both of them may be replaced.
The linkage between dye and fiber-bonding site is according to the following scheme: ##STR5## When the radical A is amino the 3-cyanoquinoline derivatives are also suitable as diazo components, which after diazotization and coupling with a coupling component KH give dyes of the formula ##STR6##
In principle, practically any desired chromophoric system can be combined with reactive groups to produce reactive dyes. Commonly used chromogens include azo, metallized azo, anthraquinone, phthalocyanine, and metal-complex formazan derivatives. Azo compounds comprise the widest range of shade from greenish-yellow to black. For yellow dyes, coupling products of pyrazolones and amino pyrazoles are commonly used. Pyridone derivatives have gained importance recently as coupling components for yellow dyes. Brilliant red colors are used based on aminohydroxynaphthalene disulfonic acids. Chromium, copper and cobalt metal-complex azo dyes made up the majority of metallized azo dyes. These dyes possess excellent light fastness. Brilliant blue and green reactive dyes with high fastness to light are the main contribution of anthraquinone derivatives. Copper and nickel phthalocyanine reactive dyes give bright turquoise shades and good wash fastness and satisfactory crocking fastness. Bright blue to green metal complex dyes from formazan derivatives are described in British Patent Nos. 1,191,741 and 1,219,383.
Additional information on the nature of the chromophoric group (the dye), the fiber, and the types of reactions involved in connecting the dye to the fiber via the bridging group is provided in Kirk-Othmer's Encyclopedia of Chemical Technology, Volume 8, "Reactive Dyes", 1979.